Effects of Defects, Flexibility, and Ozone on Stability of Metal Organic Frameworks
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Jamdade, Shubham Kailas
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Abstract
Metal−organic framework (MOF) materials are nanoporous materials whose crystalline character has made them attractive targets for synthesis of new materials and potential use in a diverse set of applications. To be commercially viable, MOFs should possess water stability because many industrial processes like gas separation and storage involve some amount of water. In this dissertation, to identify the high performing MOFs for Oxygen-Helium separations, we begin with high throughput computational screening of several thousand MOFs followed by water stability assessment of top performing MOFs for practical application. Most computational studies of MOFs consider these materials as defect free. Defects are ubiquitous in the real crystal structures of MOFs and can play strong roles in MOF water stability and subsequent degradation. Unfortunately, direct experimental detection and characterization of defects in MOFs are very challenging. We introduce a molecular simulation based approach that utilizes differences between experimentally observed and computationally predicted water stabilities of MOFs to deduce information on the presence of point defects in real materials. Further we investigate the degradation of amine functionalized adsorbents that play an important role in direct air capture (DAC) of CO2. Trace amount of atmospheric aggressive oxidants such as ozone can potentially degrade the adsorbent structure by reacting with amine sites and C-C double bonds. We use quantum chemistry calculations to examine the potential degradation of a prototypical amine-based adsorbent by ozone at a mechanistic level. Lastly, this dissertation illustrates the potential implications of diurnal variations of ambient conditions for the operation and optimization of a DAC process with process-level calculations for a specific adsorption-based process using amine-rich adsorbents. This approach highlights the necessity of understanding and adapting to real-world conditions for the successful deployment of DAC technology.
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2024-08-20
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Dissertation